WO2020110396A1 - Structure en nid d'abeilles et dispositif de purge de gaz d'échappement - Google Patents

Structure en nid d'abeilles et dispositif de purge de gaz d'échappement Download PDF

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Publication number
WO2020110396A1
WO2020110396A1 PCT/JP2019/034020 JP2019034020W WO2020110396A1 WO 2020110396 A1 WO2020110396 A1 WO 2020110396A1 JP 2019034020 W JP2019034020 W JP 2019034020W WO 2020110396 A1 WO2020110396 A1 WO 2020110396A1
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Prior art keywords
honeycomb structure
cell
cells
fluid
plugged portion
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PCT/JP2019/034020
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English (en)
Japanese (ja)
Inventor
由紀夫 宮入
昌明 桝田
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日本碍子株式会社
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Priority to DE112019005966.1T priority Critical patent/DE112019005966T5/de
Priority to CN201980067482.3A priority patent/CN113164853A/zh
Priority to JP2020558103A priority patent/JP7229272B2/ja
Publication of WO2020110396A1 publication Critical patent/WO2020110396A1/fr
Priority to US17/302,991 priority patent/US11369952B2/en

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
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    • B01D39/2075—Other inorganic materials, e.g. ceramics the material being particulate or granular sintered or bonded by inorganic agents
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/06—Ceramic, e.g. monoliths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a honeycomb structure and an exhaust gas purification device.
  • the present invention relates to a honeycomb structure and an exhaust gas purifying apparatus capable of burning and removing carbon fine particles and the like by electric heating and suppressing an increase in pressure loss.
  • Exhaust gas from automobiles usually contains fine particles such as carbon as a result of incomplete combustion. From the viewpoint of reducing health damage to the human body, there is an increasing demand for reduction of fine particles in automobile exhaust gas. At present, fine particles emitted from a gasoline engine, which is a mainstream power source for automobiles, are required to be reduced to almost zero. Further, there is a similar demand for exhaust gas particulates of diesel engines.
  • Patent Document 1 a honeycomb structure portion having porous partition walls that partition and form a plurality of cells serving as fluid channels and an outer peripheral wall positioned at the outermost periphery, and There has been proposed a honeycomb structure including a predetermined opening of the cell on the end face on the inlet side and a plugging portion arranged on the remaining opening of the cell on the end face on the outlet side of the fluid.
  • Patent Document 3 discloses that a non-conductive honeycomb cell is used without passing a current through the honeycomb structure itself. There is disclosed a method in which a metal wire is inserted into the honeycomb structure and induction heating is performed by a coil configured to circulate around the outer peripheral surface of the honeycomb structure.
  • Patent Document 3 when the technique disclosed in Patent Document 3 is applied to a honeycomb structure filter, some cells cannot be used as gas flow paths, and the filter filtration area decreases, resulting in pressure loss. was found to cause a significant increase in
  • An object of the present invention is to provide a honeycomb structure and an exhaust gas purification device that can remove carbon fine particles and the like by electric heating by combustion and suppress an increase in pressure loss.
  • a cell serving as a fluid flow path of a honeycomb structure has a plurality of cells A having openings on the fluid inflow side and a plugging portion at the end surface on the fluid outflow side, and cells. And a plurality of cells B which are arranged alternately with each other and have an outlet on the fluid outlet side and a plugging portion on the end surface on the fluid inlet side. It has been found that the above problem can be solved by configuring one or both of the plugged portions to include a magnetic material. That is, the present invention is specified as follows.
  • a porous partition wall that serves as a flow path for a fluid and defines and forms a plurality of cells that extend from an inflow end surface that is an end surface on the fluid inflow side to an outflow end surface that is an end surface on the outflow side of the fluid,
  • An outer peripheral wall located at the outermost periphery,
  • a columnar honeycomb structure having The cells are arranged alternately with a plurality of cells A having openings on the inflow side of the fluid and having plugged portions on the end surface on the outflow side of the fluid, and the outflow sides of the fluid are open.
  • a plurality of cells B each having a plugging portion on the end face on the inflow side of the fluid, One or both of the plugged portion of the cell A and the plugged portion of the cell B include a honeycomb structure.
  • the present invention it is possible to provide a honeycomb structure and an exhaust gas purifying apparatus that can remove carbon fine particles and the like by electric heating by combustion and suppress an increase in pressure loss.
  • FIG. 1 is a perspective view schematically showing a honeycomb structure of one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a cross section parallel to the cell extending direction (gas flowing direction) in the cells and partition walls having the plugged portions of the honeycomb structure of FIG. 1.
  • Fig. 3 is a cross-sectional view schematically showing a cross section parallel to a cell extending direction (gas flowing direction) in a cell and partition walls having a plugged portion of a honeycomb structure of one embodiment of the present invention.
  • Fig. 3 Fig.
  • FIG. 3 is a cross-sectional view schematically showing a cross section parallel to a cell extending direction (gas flowing direction) in a cell and partition walls having a plugged portion of a honeycomb structure of one embodiment of the present invention.
  • FIG. 3 is a schematic view of an exhaust gas flow path of an exhaust gas purification device incorporating a honeycomb structure according to an embodiment of the present invention.
  • Fig. 2 is a schematic view enlarging and describing an exhaust gas passage of an exhaust gas purifying device in which a honeycomb structure according to an embodiment of the present invention is incorporated.
  • FIG. 1 shows a perspective view schematically showing a honeycomb structure 1 of one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a cross section parallel to the cell extending direction (gas flowing direction) in the cell 15 having the plugged portions 18 and 19 and the partition wall 12 of the honeycomb structure 1 of FIG. Is listed.
  • the illustrated honeycomb structure 1 serves as a flow path for a fluid, and has a porous structure that defines a plurality of cells 15 extending from an inflow end surface 13 that is an end surface on the inflow side of the fluid to an outflow end surface 14 that is an end surface on the outflow side of the fluid.
  • the partition 12 and the outer peripheral wall 11 located at the outermost periphery are provided.
  • the cells 15 are arranged alternately with a plurality of cells A each having a plugging portion 18 on the end face on the outflow side of the fluid and an opening on the inflow side of the fluid.
  • a plurality of cells B each having an opening on the outflow side and having a plugging portion 19 on the end surface on the inflow side of the fluid are provided.
  • the cells A and the cells B are alternately arranged adjacent to each other with the partition wall 12 interposed therebetween, and both end surfaces form a checkered pattern.
  • the number, arrangement, shape, etc. of the cells A and B and the thickness of the partition walls 12 are not limited, and can be appropriately designed as necessary.
  • Such a honeycomb structure 1 can be used as a filter (honeycomb filter) for purifying exhaust gas.
  • the plugging portion 18 of the cell A having the plugging portion 18 on the end surface on the fluid outflow side opening and the fluid outflow side is the plugging portion of a conventionally known honeycomb structure. It is possible to use the one configured similarly to the one used as the section.
  • the plugged portion 19 of the cell B having the plugged portion 19 on the end surface on the fluid inflow side that is open on the outflow side of the fluid contains a magnetic material.
  • the plugging portion 19 of the cell B may have a material used as a plugging portion of a conventionally known honeycomb structure as a base material, and the base material may include a magnetic material, or may be composed of only a magnetic material. Good.
  • the plugging portion 19 of the cell B contains the magnetic substance, but the present invention is not limited to this, and the plugging portion 18 of the cell A and the plugging portion 19 of the cell B are not limited thereto. It is sufficient that one or both contain a magnetic material.
  • the plugged portion 18 of the cell A and the plugged portion 19 of the cell B may include glass.
  • the plugged portions 18 and 19 of the cells A and B may be disposed after the outer peripheral coating is formed, or may be in a state before the outer peripheral coating is formed, that is, a honeycomb structure. It may be arranged at the stage of producing the body 1.
  • the plugged portions 18 of the cells A and the plugged portions 19 of the cells B By configuring one or both of the plugged portions 18 of the cells A and the plugged portions 19 of the cells B to include a magnetic material, the plugged portions when the honeycomb structure 1 is used as a honeycomb filter are Since the magnetic material is included as it is, it is not necessary to use the cells 15 of the honeycomb structure 1 only to fill the material containing the magnetic material, and as a result, an increase in pressure loss can be suppressed. Further, in the illustrated honeycomb structure 1, the cell B has a plugging portion 19 including a magnetic material on the end surface on the fluid inflow side.
  • the coil wiring that spirals around the outer periphery of the honeycomb structure 1 is arranged at a position corresponding to the plugging portion 19 of the cell B. That is, by only arranging the coil wiring so as to spirally rotate around the outer periphery in the vicinity of the end surface on the fluid inflow side of the honeycomb structure 1 and performing induction heating, the heat from the end surface heated on the inflow side moves the fluid. At the same time, it propagates through the partition 12 and the cell 15 and is heated to the outflow side. Therefore, it is not necessary to heat the entire honeycomb structure 1 in the length direction, and the energy efficiency is improved.
  • the coil wiring that spirals around the outer periphery of the honeycomb structure 1 is arranged at the position corresponding to the plugging portion 19 of the cell B as described above, but the present invention is not limited to this.
  • the wiring may be provided at a position corresponding to one or both of the plugged portion 18 of the cell A and the plugged portion 19 of the cell B.
  • the plugging portions arranged at the positions corresponding to the coil wirings include a magnetic material.
  • the depth of the plugging portion 19 of the cell B containing the magnetic material in the cell extending direction gradually decreases from the center of the honeycomb structure 1 toward the outermost periphery. ..
  • the coil wiring is arranged at a position corresponding to the plugging portion 19 of the cell B, that is, the outer periphery is spirally wound around the end face on the fluid inflow side of the honeycomb structure 1.
  • the heat due to the induction heating is hard to be blocked by the outer plugging portion 19, and the honeycomb structure 1 is well heated to the center.
  • the form gradually decreasing from the center of the honeycomb structure 1 to the outermost periphery is not particularly limited and can be appropriately designed. For example, at a uniform rate from the center of the honeycomb structure 1 toward the outermost periphery. Those that are smaller are preferable.
  • the depth of the plugging portion 19 of the cell B containing the magnetic material in the cell extending direction gradually decreases from the center of the honeycomb structure 1 toward the outermost periphery as described above.
  • the present invention is not limited to this, and the depth in the direction in which one or both of the plugged portions 18 of the cells A and the plugged portions 19 of the cells B containing the magnetic material is the center of the honeycomb structure 1. It may be gradually decreased from the outermost position to the outermost position.
  • one or both of the plugged portion 18 of the cell A and the plugged portion 19 of the cell B containing the magnetic material may have a depth in the extending direction of the cells appropriately adjusted to a desired purpose. You may form so that it may change toward the outermost periphery from the center of.
  • the Curie point of the magnetic material is not particularly limited, but it is preferably 700°C or higher.
  • the Curie point of the magnetic material may be 800° C. or higher.
  • the Curie point of the magnetic material is 700° C. or higher, it becomes possible to reach the honeycomb temperature sufficient to raise the catalyst temperature above the catalyst activation temperature, and of course the PM(s) trapped in the cells 15 ( It becomes easy to regenerate the honeycomb structure filter by burning away the particulate matter).
  • an alloy containing Fe or Co as a main component is suitable, and a specific composition is, for example, balance Co-20 mass% Fe, balance Co-25 mass%.
  • Ni-4 mass% Fe balance Fe-15 to 35 mass% Co, balance Fe-17 mass% Co-2 mass% Cr-1 mass% Mo, balance Fe-49 mass% Co-2 mass% V, balance Fe -18 mass% Co-10 mass% Cr-2 mass% Mo-1 mass% Al, balance Fe-27 mass% Co-1 mass% Nb, balance Fe-20 mass% Co-1 mass% Cr-2 mass% V, balance Fe-35 mass% Co-1 mass% Cr, pure cobalt, pure iron, electromagnetic soft iron, balance Fe-0.1 to 0.5 mass% Mn and the like.
  • the Curie point of a magnetic material refers to the temperature at which the ferromagnetic properties are lost.
  • the material of the partition walls 12 and the outer peripheral wall 11 of the honeycomb structure 1 is not particularly limited, but since it is necessary to be a porous body having a large number of pores, it is usually formed of a ceramic material.
  • a ceramic material for example, cordierite, silicon carbide, aluminum titanate, silicon nitride, mullite, alumina, silicon-silicon carbide-based composite material, silicon carbide-cordierite-based composite material, particularly silicon-silicon carbide composite material or silicon carbide And a sintered body.
  • silicon carbide-based means that the honeycomb structure 1 contains silicon carbide in an amount of 50 mass% or more of the entire honeycomb structure 1.
  • the honeycomb structure 1 contains a silicon-silicon carbide composite material as a main component means that the honeycomb structure 1 contains 90 mass% or more of the silicon-silicon carbide composite material (total mass) of the whole honeycomb structure 1.
  • the silicon-silicon carbide composite material contains silicon carbide particles as an aggregate and silicon as a binder for bonding the silicon carbide particles, and a plurality of silicon carbide particles are formed between the silicon carbide particles. It is preferably bound by silicon so as to form pores.
  • the fact that the honeycomb structure 1 contains silicon carbide as a main component means that the honeycomb structure 1 contains silicon carbide (total mass) in an amount of 90 mass% or more of the whole honeycomb structure 1.
  • the ceramic material is at least one selected from the group consisting of cordierite, silicon carbide, aluminum titanate, silicon nitride, mullite, and alumina.
  • the cell shape of the honeycomb structure 1 is not particularly limited, it is preferably a polygon such as a triangle, a quadrangle, a pentagon, a hexagon, and an octagon, a circle, or an ellipse in a cross section orthogonal to the central axis, and other It may be a fixed form.
  • the outer shape of the honeycomb structure 1 is not particularly limited, but the end face is a circular column (cylindrical shape), the end face is an oval column, and the end face is a polygon (square, pentagon, hexagon, heptagon, octagon). And the like).
  • the size of the honeycomb structure 1 is not particularly limited, but the length in the central axis direction is preferably 40 to 500 mm. Further, for example, when the honeycomb structure 1 has a cylindrical outer shape, it is preferable that the radius of the end face be 50 to 500 mm.
  • the thickness of the partition walls 12 of the honeycomb structure 1 is preferably 0.20 to 0.50 mm, and more preferably 0.25 to 0.45 mm from the viewpoint of ease of manufacturing. For example, when it is 0.20 mm or more, the strength of the honeycomb structure 1 is further improved, and when it is 0.50 mm or less, the pressure loss can be made smaller when the honeycomb structure 1 is used as a filter. ..
  • the thickness of the partition wall 12 is an average value measured by a method of observing a cross section in the central axis direction with a microscope.
  • the porosity of the partition walls 12 constituting the honeycomb structure 1 is preferably 30 to 70%, and more preferably 40 to 65% from the viewpoint of ease of production. When it is 30% or more, the pressure loss tends to decrease, and when it is 70% or less, the strength of the honeycomb structure 1 can be maintained.
  • the average pore diameter of the porous partition wall 12 is preferably 5 to 30 ⁇ m, more preferably 10 to 25 ⁇ m. When it is 5 ⁇ m or more, the pressure loss can be reduced when it is used as a filter, and when it is 30 ⁇ m or less, the strength of the honeycomb structure 1 can be maintained.
  • the terms "average pore size” and “porosity” mean the average pore size and porosity measured by the mercury porosimetry method.
  • the cell density of the honeycomb structure 1 is also not particularly limited, but is preferably in the range of 5 to 63 cells/cm 2 , and more preferably 31 to 54 cells/cm 2 .
  • Such a honeycomb structure 1 is formed into a honeycomb shape having partition walls 12 that form a plurality of cells 15 that pass through a kneaded material containing a ceramic raw material from one end surface to the other end surface and serve as fluid passages. Then, the honeycomb formed body is formed, and the honeycomb formed body is dried and then fired.
  • the outer peripheral wall may be extruded integrally with the honeycomb structure portion and used as it is as the outer peripheral wall, or it may be molded or fired.
  • the outer periphery of the honeycomb formed body may be ground into a predetermined shape, and a coating material may be applied to the honeycomb structure whose outer periphery has been ground to form an outer peripheral coating.
  • a honeycomb structure having an outer periphery is used without grinding the outermost periphery of the honeycomb structure, and the outer peripheral surface of the honeycomb structure having the outer periphery (that is, The outer peripheral coating may be formed by further applying the coating material to the outer periphery of the honeycomb structure).
  • the outer peripheral wall 11 of the two-layer structure which is located at the outermost periphery, is formed in which the outer peripheral coating of the coating material is further laminated on the outer peripheral surface of the honeycomb structure.
  • the outer peripheral wall may be extruded integrally with the honeycomb structure part and fired as it is, and may be used as the outer peripheral wall without processing the outer periphery.
  • the composition of the coating material is not particularly limited, and various known coating materials can be appropriately used.
  • the coating material may further contain colloidal silica, an organic binder, clay and the like.
  • the organic binder is preferably used in an amount of 0.05 to 0.5% by mass, more preferably 0.1 to 0.2% by mass.
  • Clay is preferably used in an amount of 0.2 to 2.0% by mass, more preferably 0.4 to 0.8% by mass.
  • the honeycomb structure 1 is not limited to the integral type honeycomb structure 1 in which the partition walls 12 are integrally formed.
  • the honeycomb structure 1 has porous partition walls 12, and the partition walls 12 allow passage of fluid.
  • a honeycomb structure 1 having a structure in which a plurality of columnar honeycomb segments in which a plurality of cells 15 to be defined are formed and combined through a bonding material layer (hereinafter, may be referred to as “bonded honeycomb structure”) May be
  • the honeycomb structure 1 of the present embodiment may have a catalyst supported on the surface of the porous partition walls 12 forming the inner walls of the plurality of cells 15 and/or in the pores of the partition walls 12.
  • the honeycomb structure 1 of the present embodiment has a catalyst carrier carrying a catalyst and a filter provided with plugging portions 18 and 19 for purifying particulate matter (carbon fine particles) in exhaust gas (for example, It may be configured as a diesel particulate filter (hereinafter, also referred to as "DPF").
  • DPF diesel particulate filter
  • the type of catalyst is not particularly limited, and can be appropriately selected depending on the intended use or application of the honeycomb structure 1.
  • a noble metal catalyst or a catalyst other than these may be used.
  • a noble metal-based catalyst a noble metal such as platinum (Pt), palladium (Pd), or rhodium (Rh) is supported on the surface of alumina fine pores, and a three-way catalyst or an oxidation catalyst containing a cocatalyst such as ceria or zirconia, or an alkali is used.
  • a NO x storage reduction catalyst LNT catalyst
  • NO x selective reduction catalyst containing copper substituted or iron-substituted zeolite (SCR catalyst) and the like As a catalyst without using a noble metal, NO x selective reduction catalyst containing copper substituted or iron-substituted zeolite (SCR catalyst) and the like. Further, two or more kinds of catalysts selected from the group consisting of these catalysts may be used.
  • the method for supporting the catalyst is not particularly limited, and it can be performed according to the conventional supporting method for supporting the catalyst on the honeycomb structure.
  • Each of the fired honeycomb structures can be used as a honeycomb segment, and the side surfaces of a plurality of honeycomb segments can be bonded and integrated with a bonding material to form a honeycomb structure in which the honeycomb segments are bonded.
  • the honeycomb structure in which the honeycomb segments are joined can be manufactured, for example, as follows. The bonding material is applied to the bonding surface (side surface) with the bonding material adhesion prevention mask attached to both bottom surfaces of each honeycomb segment.
  • honeycomb segments are arranged adjacent to each other so that the side surfaces of the honeycomb segments face each other, and the adjacent honeycomb segments are pressure-bonded to each other and then dried by heating.
  • the outer peripheral portion may be ground to have a desired shape (for example, a columnar shape), the outer peripheral surface may be coated with a coating material, and the outer peripheral wall 11 may be formed by heating and drying.
  • the material of the mask for preventing adhesion of the bonding material is not particularly limited, but for example, synthetic resin such as polypropylene (PP), polyethylene terephthalate (PET), polyimide, or Teflon (registered trademark) can be preferably used.
  • the mask preferably has an adhesive layer, and the material of the adhesive layer is acrylic resin, rubber type (for example, rubber containing natural rubber or synthetic rubber as a main component), or silicon type resin. preferable.
  • An adhesive film having a thickness of 20 to 50 ⁇ m, for example, can be preferably used as the bonding material adhesion preventing mask.
  • the bonding material for example, a material prepared by mixing ceramic powder, a dispersion medium (for example, water, etc.), and, if necessary, an additive such as a binder, a deflocculant, and a foamed resin can be used.
  • a dispersion medium for example, water, etc.
  • an additive such as a binder, a deflocculant, and a foamed resin
  • the ceramics should contain at least one selected from the group consisting of cordierite, mullite, zircon, aluminum titanate, silicon carbide, silicon nitride, zirconia, spinel, indialite, sapphirine, corundum, and titania. Is preferable, and the same material as that of the honeycomb structure is more preferable.
  • the binder include polyvinyl alcohol, methyl cellulose, CMC (carboxymethyl cellulose) and the like.
  • the honeycomb structure 1 may have a surface layer on at least a part of the surface of the partition wall 12.
  • the surface layer contains a magnetic material and is breathable.
  • having air permeability means that the permeability of the surface layer is 1.0 ⁇ 10 ⁇ 13 m 2 or more. From the viewpoint of further reducing the pressure loss, the permeability is preferably 1.0 ⁇ 10 ⁇ 12 m 2 or more. Since the surface layer has air permeability, pressure loss due to the surface layer can be suppressed.
  • permeability refers to a physical property value calculated by the following formula (1), and is a value serving as an index representing a passage resistance when a predetermined gas passes through the substance (partition wall 12). is there.
  • C permeability (m 2 )
  • F gas flow rate (cm 3 /s)
  • T sample thickness (cm)
  • V gas viscosity (dynes ⁇ sec/cm 2 ).
  • D indicates the sample diameter (cm)
  • P indicates the gas pressure (PSI).
  • the partition wall 12 with the surface layer is cut out, the permeability is measured with the surface layer attached, and then the permeability measurement is performed with the surface layer scraped off.
  • the permeability of the surface layer is calculated from the ratio of the thickness of the base material and the permeability measurement results.
  • the surface layer contains the magnetic material, the heat propagated by the induction heating of the plugging portion 19 containing the magnetic material heats the surface layer, so that the honeycomb structure 1 can be heated by the electromagnetic induction even better.
  • the magnetic material contained in the surface layer may be made of the same material as the magnetic material contained in the plugging portion 19 described above.
  • the porosity of the surface layer is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. By having a porosity of 50% or more, pressure loss can be suppressed. However, if the porosity is too high, the surface layer becomes brittle and peels off easily, so 90% or less is preferable.
  • the porosity of the surface layer is calculated from the measured mass and the mercury porosity curve.
  • the porosity of the surface layer may be calculated from the area ratio of the void portion and the solid portion by performing SEM image photographing and analyzing the image of the surface layer portion.
  • the average pore diameter of the surface layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, further preferably 4 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the average pore diameter is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, further preferably 4 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the mercury porosi curve with the surface layer (pore volume frequency) and only the surface layer were scraped off in the form of the peak value with a mercury porosimeter.
  • the difference between the mercury porosicurves of only the substrate is the mercury porosicurve of the surface layer, and the peak is the average pore diameter.
  • binarization of voids and solid portions is performed, 20 or more voids are randomly selected, and the average of the inscribed circles is selected. May be the average pore diameter.
  • the weight average particle diameter is preferably 20 ⁇ m or less.
  • the weight average particle diameter is not particularly set, but can be set to 0.5 ⁇ m or more, for example.
  • the weight average particle diameter is measured by a laser diffraction type particle size distribution measuring device.
  • the shortest diameter d of the magnetic particles is 0.1 to 5 ⁇ m and the longest diameter of the magnetic body is L ⁇ m.
  • the shortest diameter d means that the largest line segment among the 50 line segments that is orthogonal to the longest diameter of 50 particles by image analysis from SEM images is the shortest diameter of the particles, and this is averaged by the number of particles. Therefore, the shortest diameter d can be obtained.
  • the length is obtained by averaging the longest diameters of 50 or more particles in the SEM image with the number of particles to obtain the longest diameter L.
  • the magnetic material is needle-shaped. Needle-like means L/d ⁇ 5.
  • the thickness of the surface layer is not particularly limited. However, in order to obtain the effect of the surface layer more remarkably, the thickness of the surface layer is preferably 10 ⁇ m or more. On the other hand, from the viewpoint of avoiding an increase in pressure loss, the thickness of the surface layer is preferably 80 ⁇ m or less. The thickness of the surface layer is more preferably 50 ⁇ m or less.
  • the honeycomb structure 1 on which the surface layer is formed is cut in a direction perpendicular to the direction in which the cells 15 extend, and the thickness of the surface layer is measured from the cross section, and an arbitrary 5 is obtained. An average of the point thickness measurements can be taken.
  • FIG. 3 is a cross section of the cell 25 having the plugged portions 28 and 29 and the partition wall 22 of the honeycomb structure 10 according to another embodiment of the present invention, which is parallel to the cell extending direction (gas flowing direction).
  • the cross-sectional view which shows typically is described.
  • the plugging portion 29 of the cell B having an opening on the fluid outflow side is made of a material containing a magnetic material. Therefore, when the honeycomb structure 10 is used as a honeycomb filter, the plugged portion contains the magnetic material as it is, and it is necessary to use the cells 25 of the honeycomb structure 10 only to fill the material containing the magnetic material. Disappears. As a result, an increase in pressure loss can be suppressed.
  • the opening of the cell B having the plugging portion 29 on the end surface of the fluid inflow side and the fluid inflow side is open, and the opening of the fluid inflow side is the end surface on the fluid outflow side. It is smaller than the opening of the cell A having the plugged portion 28 at the bottom, and the plugged portion 29 of the cell B contains a magnetic material. According to such a configuration, in the exhaust gas purifying apparatus using the honeycomb structure 10, a larger amount of fluid can be taken in from the cell A in which the inflow side of the fluid is larger open, and the cell B is in the inflow side of the fluid.
  • the coil wiring that spirals around the outer periphery of the honeycomb structure 10 is arranged at a position corresponding to the plugging portion 29 of the cell B, that is, the honeycomb structure 10
  • the coil wiring is arranged so as to spirally rotate around the outer periphery in the vicinity of the end surface on the inflow side of the fluid, and the heat from the end surface heated on the inflow side is moved along with the movement of the fluid and the partition wall 22 and the cell 25. It propagates inside and is heated to the outflow side. Therefore, it is not necessary to heat the entire honeycomb structure 10 in the longitudinal direction, and the energy efficiency is improved.
  • the opening of the cell B is smaller than the opening of the cell A as described above, but the present invention is not limited to this, and the opening of the cell A and the opening of the cell B are formed in different sizes.
  • the plugged portion 28 of the cell A or the plugged portion 29 of the cell B having the smaller opening may be made of a material containing a magnetic material.
  • FIG. 4 is a cross section of the cell 35 having the plugged portions 38 and 39 and the partition wall 32 of the honeycomb structure 30 according to another embodiment of the present invention, which is parallel to the cell extending direction (gas flowing direction).
  • the cross-sectional view which shows typically is described.
  • the opening of the cell B having the plugging portion 39 on the end face on the fluid inflow side and the fluid outflow side is open, and the cell B on the fluid inflow side is open on the end face on the fluid outflow side. It is formed to have substantially the same size as the opening of the cell A having the sealing portion 38, and the plugging portion 39 of the cell B is made of a material containing a magnetic material.
  • the depth of the plugged portions 39 of the cells B in the cell extending direction is substantially the same from the center to the outer periphery of the honeycomb structure 30.
  • the plugging portion 39 of the cell B With a material containing a magnetic material, the plugging portion when the honeycomb structure 30 is used as a honeycomb filter contains the magnetic material as it is, and thus contains the magnetic material. It is no longer necessary to use the cells 35 of the honeycomb structure 30 solely for filling the material. As a result, an increase in pressure loss can be suppressed.
  • the cell B has a plugging portion 39 including a magnetic material on the end surface on the fluid inflow side. Therefore, when the honeycomb structure 30 is used as the exhaust gas purifying apparatus, the same arrangement configuration as that described in the exhaust gas purifying apparatus 6 using the honeycomb structure 1 can be used.
  • FIG. 5 is a schematic diagram of an exhaust gas flow path of the exhaust gas purification device 6 in which the honeycomb structure 1 is incorporated.
  • the exhaust gas flow path having the honeycomb structure 1 and the coil wiring 4 that spirals around the outer periphery of the honeycomb structure 1 may be defined by the metal tube 2.
  • the exhaust gas purification device 6 can be arranged on the expanded diameter portion 2 a of the metal pipe 2.
  • the coil wiring 4 may be fixed in the metal tube 2 by the fixing member 5.
  • the fixing member 5 is preferably a heat resistant member such as ceramic fiber.
  • the honeycomb structure 1 may carry a catalyst.
  • the coil wiring 4 is spirally wound around the outer periphery of the honeycomb structure 1.
  • a mode in which two or more coil wires 4 are used is also envisioned.
  • An alternating current supplied from the alternating current power source CS flows to the coil wiring 4 in response to the turning on of the switch SW, and as a result, a magnetic field that periodically changes is generated around the coil wiring 4.
  • the control unit 3 controls ON/OFF of the switch SW.
  • the control unit 3 can turn on the switch SW in synchronism with the start of the engine to allow an alternating current to flow through the coil wiring 4. It is also assumed that the control unit 3 turns on the switch SW regardless of the start of the engine (for example, in response to the operation of the heating switch pressed by the driver).
  • the honeycomb structure 1 is heated according to the change in the magnetic field according to the alternating current flowing through the coil wiring 4. As a result, carbon fine particles and the like collected by the honeycomb structure 1 are burned.
  • the honeycomb structure 1 carries a catalyst
  • the temperature rise of the honeycomb structure 1 raises the temperature of the catalyst carried by the catalyst carrier contained in the honeycomb structure 1 to promote the catalytic reaction.
  • carbon monoxide (CO), nitride oxide (NO x ), hydrocarbon (CH) are oxidized or reduced to carbon dioxide (CO 2 ), nitrogen (N 2 ), water (H 2 O).
  • FIG. 6 is a schematic view enlarging and describing an exhaust gas flow path of the exhaust gas purification device 26 in which the honeycomb structure 10 is incorporated.
  • the flow path of the exhaust gas has the honeycomb structure 10 and the coil wiring 24 that spirals around the outer periphery of the honeycomb structure 10.
  • the flow path of the exhaust gas is defined by the metal pipe 27, and the exhaust gas purification device 26 can be arranged in the expanded diameter portion 27 a of the metal pipe 27.
  • the coil wiring 24 is fixed in the metal tube 27 by a fixing member 25 made of a heat resistant material such as ceramic fiber.
  • the cell B has the plugging portion 29 containing the magnetic material on the fluid inflow side, and the outer periphery of the honeycomb structure 10 is surrounded.
  • the coil wiring 24 that spirals around is arranged at a position corresponding to the plugged portion 29 of the cell B. That is, induction heating is performed by arranging the coil wiring 24 so as to spirally rotate around the outer periphery only in the vicinity of the end face on the fluid inflow side of the honeycomb structure 10.
  • the heat from the end surface heated on the inflow side propagates in the partition walls 22 and the cells 25 as the fluid moves, and is heated to the outflow side. As a result, it is not necessary to heat the entire honeycomb structure 10 in the length direction, and energy efficiency is improved.
  • a honeycomb structure having porous partition walls and a plurality of cells partitioned by the partition walls is manufactured.
  • a cordierite-forming raw material is prepared as a material for kneaded clay.
  • each component is blended so as to have a theoretical composition of cordierite crystals, and thus a silica source component, a magnesia source component, an alumina source component and the like are blended.
  • quartz and fused silica are preferably used as the silica source component, and the particle size of the silica source component is preferably 100 to 150 ⁇ m.
  • magnesia source component examples include talc and magnesite. Of these, talc is preferred. Talc is preferably contained in the cordierite forming raw material in an amount of 37 to 43% by mass.
  • the particle size (average particle size) of talc is preferably 5 to 50 ⁇ m, more preferably 10 to 40 ⁇ m.
  • the magnesia (MgO) source component may contain Fe 2 O 3 , CaO, Na 2 O, K 2 O and the like as impurities.
  • alumina source component those containing at least one of aluminum oxide and aluminum hydroxide are preferable from the viewpoint of less impurities.
  • aluminum hydroxide is preferably contained in an amount of 10 to 30% by mass, and aluminum oxide is preferably contained in an amount of 0 to 20% by mass.
  • the clay material (additive) to be added to the cordierite-forming raw material At least a binder and a pore-forming agent are used as additives. In addition to the binder and the pore-forming agent, a dispersant or a surfactant can be used.
  • a substance capable of reacting with oxygen to be oxidized and removed at a temperature below the firing temperature of cordierite, or a low melting point reaction substance having a melting point at a temperature below the firing temperature of cordierite can be used.
  • the substance that can be removed by oxidation include resin (particularly particulate resin) and graphite (particularly particulate graphite).
  • the low-melting-point reactant is at least one metal selected from the group consisting of iron, copper, zinc, lead, aluminum, and nickel, and an alloy mainly containing these metals (for example, carbon steel in the case of iron). Or cast iron, stainless steel), or an alloy containing two or more kinds as main components.
  • the low melting point reaction substance is preferably a powdery or fibrous iron alloy. Further, the particle diameter or fiber diameter (average diameter) is preferably 10 to 200 ⁇ m.
  • the shape of the low-melting-point reaction substance include a spherical shape, a curl rhombus shape, and a ganpe sugar shape. These shapes are preferable because the shape of the pores can be easily controlled.
  • binder examples include hydroxypropylmethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol and the like.
  • dispersant examples include dextrin, polyalcohol and the like.
  • surfactant examples include fatty acid soap. The additives may be used alone or in combination of two or more.
  • the prepared kneaded material is molded into a honeycomb shape by an extrusion molding method, an injection molding method, a press molding method or the like to obtain a raw honeycomb molded body. It is preferable to employ the extrusion molding method because continuous molding is easy and, for example, cordierite crystals can be oriented.
  • the extrusion molding method can be carried out using a device such as a vacuum clay kneader, a ram type extrusion molding machine, or a twin screw type continuous extrusion molding machine.
  • the honeycomb formed body is dried and adjusted to a predetermined size to obtain a dried honeycomb body.
  • the honeycomb formed body can be dried by hot air drying, microwave drying, dielectric drying, reduced pressure drying, vacuum drying, freeze drying, or the like. Since the whole can be dried quickly and uniformly, it is preferable to perform drying by combining hot air drying and microwave drying or dielectric drying.
  • the material of the plugging portion (slurry for plugging), the same material for kneaded material as the partition wall (honeycomb dried body) may be used, or a different material may be used. Specifically, it is obtained by mixing a ceramic raw material, a surfactant, and water, adding a sintering aid, a pore-forming agent, etc., if necessary, to form a slurry, and kneading using a mixer or the like. be able to.
  • a mask is applied to a part of the cell openings on one end surface of the honeycomb dried body, and the end surface is immersed in a storage container in which the plugging slurry is stored, and the cells are not masked. Fill plugging slurry.
  • a mask is applied to a part of the cell openings on the other end surface of the dried honeycomb body, and the end surface is immersed in a storage container in which the plugging slurry is stored, and the cells are not masked. Then, the plugging slurry is filled. Then, the honeycomb structure having a plugged portion is obtained by drying and firing.
  • the drying condition the same condition as the condition for drying the honeycomb formed body can be adopted.
  • the above-mentioned firing conditions can be usually set to a temperature of 1410 to 1440° C. for 3 to 15 hours in an air atmosphere.
  • the plugging slurry in which the cell openings on one or both end faces are immersed contains a magnetic substance.
  • one or both of the plugged portion of the cell A and the plugged portion of the cell B of the honeycomb structure contains the magnetic material.
  • the outer peripheral surface when the obtained honeycomb structure is manufactured in a state where the outer peripheral wall is formed on the outer peripheral surface thereof, the outer peripheral surface may be ground and the outer peripheral wall may be removed.
  • a coating material is applied to the outer periphery of the honeycomb structure from which the outer peripheral wall is removed in this manner to form an outer peripheral coating.
  • the outer peripheral surface when the outer peripheral surface is ground, a part of the outer peripheral wall may be ground and removed, and the outer peripheral coating may be formed on the part by a coating material.
  • the coating material for example, it can be prepared using a two-axis rotating vertical mixer.
  • the coating material may further contain colloidal silica, organic binder, clay and the like.
  • the organic binder is preferably used in an amount of 0.05 to 0.5% by mass, more preferably 0.1 to 0.2% by mass.
  • Clay is preferably used in an amount of 0.2 to 2.0% by mass, more preferably 0.4 to 0.8% by mass.
  • a coating material is applied to the outer peripheral surface of the honeycomb structure prepared above, and the applied coating material is dried to form an outer peripheral coating.
  • the honeycomb structure is placed on a rotary table and rotated, and the coating nozzle is discharged along the outer peripheral portion of the honeycomb structure while discharging the coating material from the blade-shaped coating nozzle.
  • a method of applying by pressing can be mentioned. With this configuration, the coating material can be applied with a uniform thickness. Further, the surface roughness of the formed outer peripheral coating becomes small, and it is possible to form an outer peripheral coating which has an excellent appearance and is not easily damaged by thermal shock.
  • a coating material is applied to the entire outer peripheral surface of the honeycomb structure to form an outer peripheral coating.
  • a coating material may be partially applied to form the outer peripheral coating, Of course, a coating material may be applied to the entire outer peripheral surface of the honeycomb structure to form the outer peripheral coating.
  • the method for drying the applied coating material that is, the undried outer peripheral coating
  • the coating material that is, the undried outer peripheral coating
  • a method of removing water and organic matter by holding at 600° C. for 1 hour or more in an electric furnace can be preferably used.
  • the cell openings of the honeycomb structure are not sealed in advance, the cell openings may be plugged after the outer peripheral coating is formed.
  • the silicon carbide powder contained in the coating material is colored by irradiating the outer peripheral surface with a laser, the outer peripheral coating of the obtained honeycomb structure is irradiated with laser light.
  • the product information may be printed (marked).
  • Suitable examples of the laser beam used for laser marking include carbon dioxide (CO 2 ) laser, YAG laser, and YVO4 laser.
  • the conditions of the laser for irradiating the laser beam can be appropriately selected according to the type of the laser used. For example, when a CO 2 laser is used, the output is 15 to 25 W and the scanning speed is 400 to 600 mm/ Marking with s is preferred. By marking in this way, the irradiated part develops a color such that it exhibits a dark color such as black to green, and the contrast due to the coloring with the non-irradiated part becomes extremely good.
  • the method of supporting the catalyst is not particularly limited, and it can be carried out according to the method of supporting the catalyst which is used in the conventional method for manufacturing a honeycomb structure.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Geometry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Filtering Materials (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

L'invention concerne une structure en nid d'abeilles et un dispositif de purge de gaz d'échappement qui sont capables de brûler et d'éliminer des particules de carbone par chauffage électrique et qui présentent une suppression d'augmentation de perte de pression. Cette structure en nid d'abeilles colonnaire comprend : des parois de séparation poreuses qui délimitent et forment une pluralité de cellules servant de canaux d'écoulement pour un fluide et s'étendant chacune à partir d'une surface d'extrémité d'entrée qui est la surface d'extrémité du côté entrée de fluide à une surface d'extrémité de sortie qui est la surface d'extrémité du côté sortie de fluide ; et une paroi périphérique externe située au niveau de la périphérie la plus à l'extérieur. Les cellules comprennent : une pluralité de cellules A qui sont chacune ouvertes sur le côté entrée de fluide et comportent chacune une partie à ouverture scellée au niveau de la surface d'extrémité du côté sortie de fluide ; et une pluralité de cellules B qui sont agencées en alternance par rapport aux cellules A, sont chacune ouvertes sur le côté sortie de fluide, et comportent chacune une partie à ouverture scellée au niveau de la surface d'extrémité du côté entrée de fluide. L'une ou les deux parties à ouverture scellée de chacune des cellules A et la partie à ouverture scellée de chacune des cellules B comprennent un corps magnétique.
PCT/JP2019/034020 2018-11-30 2019-08-29 Structure en nid d'abeilles et dispositif de purge de gaz d'échappement WO2020110396A1 (fr)

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DE112019005966.1T DE112019005966T5 (de) 2018-11-30 2019-08-29 Wabenstruktur und Abgasreinigungsvorrichtung
CN201980067482.3A CN113164853A (zh) 2018-11-30 2019-08-29 蜂窝结构体及废气净化装置
JP2020558103A JP7229272B2 (ja) 2018-11-30 2019-08-29 ハニカム構造体及び排気ガス浄化装置
US17/302,991 US11369952B2 (en) 2018-11-30 2021-05-18 Honeycomb structure and exhaust gas purifying device

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JP2018-225822 2018-11-30

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WO2022097341A1 (fr) * 2020-11-04 2022-05-12 日本碍子株式会社 Support de catalyseur et système de catalyseur de chauffage par induction
WO2022118531A1 (fr) * 2020-12-02 2022-06-09 日本碍子株式会社 Structure en nid d'abeilles, dispositif de purification de gaz d'échappement, et procédé de production de structure en nid d'abeilles

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CN113164853A (zh) 2021-07-23
DE112019005966T5 (de) 2021-08-19

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